CN100396729C - Thermoset composition, method for the preparation thereof, and articles prepared therefrom - Google Patents
Thermoset composition, method for the preparation thereof, and articles prepared therefrom Download PDFInfo
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- CN100396729C CN100396729C CNB2004800175532A CN200480017553A CN100396729C CN 100396729 C CN100396729 C CN 100396729C CN B2004800175532 A CNB2004800175532 A CN B2004800175532A CN 200480017553 A CN200480017553 A CN 200480017553A CN 100396729 C CN100396729 C CN 100396729C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
Abstract
A curable composition includes a poly(arylene ether) and a fused alicyclic (meth)acrylate monomer. Also described are a method of preparing the composition, a cured composition derived from the curable composition, and an article comprising the cured composition. The composition is useful, for example, as a bulk molding compound.
Description
Background technology
Thermoset composition is used for a large amount of technology that goods are made, and for example comprises resin transfer molding, sheet molding, Unitarily molded (bulk molding), pulls out moulding (pultrusion), injection moulding (comprise the gentle pressing mold of reaction injection molding(RIM) mould (atmospheric pressure molding)) or the like.The thermoset composition that comprises polyarylene ether resin (non-functionalized with functionalized) has been described.For example, people's such as Tracy United States Patent (USP) 6,051,662 has been described curable compositions and has been comprised thermosetting resin and the non-functionalized poly arylene ether of lower molecular weight resin.People's such as Zarnoch United States Patent (USP) 6,521,703 has been described curable resin composition and has been comprised unsaturated polyester, alkenyl aromatic compounds and end-blocking poly (arylene ether).As another example, people's such as Yeager United States Patent (USP) 6,352,782 has been described the composition that comprises end capped blocking polyphenyl ether resin of reaction and curable unsaturated monomer component.
Still need to have the thermoset composition of the dielectric properties of improvement.
The invention summary
The curable compositions that shows the dielectric properties with improvement comprises poly (arylene ether) and condenses alicyclic (methyl) acrylate monomer.
Other embodiment is described below, comprises the method for preparing curable compositions, the reaction product that obtains from curable compositions and the goods that comprise curable compositions.
Preferred implementation
A kind of embodiment is a curable compositions, comprises poly (arylene ether) and condenses alicyclic (methyl) acrylate monomer.The polyarylene ether resin can right and wrong functionalized or functionalized.
Non-functionalized poly arylene ether resin can be directly from the polymerization of monohydroxy phenols and obtain." not end capped " described herein or " non-functionalized " poly (arylene ether) comprises the repeated structural unit with following formula,
Wherein for each structural unit, each Z
1Be halogen, uncle or secondary C independently
1-C
12Alkyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like; Each Z
2Be hydrogen, halogen, uncle or secondary C independently
1-C
12Alkyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like.Preferably, each Z
1Be C
1-4Alkyl and each Z
2Be hydrogen or methyl.
Comprise poly (arylene ether) homopolymer or multipolymer.Preferred homopolymer is to contain 2, those of 6-dimethyl-phenylene ether units.Suitable copolymers comprises random copolymers, for example contains with 2,3, and 6-trimethylammonium-1,4-phenylene ether units bonded 2,6-dimethyl-phenylene ether units, or from 2 and 2,3, the multipolymer that the copolyreaction of 6-pseudocuminol obtains.
Non-functionalized poly arylene ether generally can pass through at least a list-hydroxy-aromatic compound, as 2 or 2,3, and the oxidative coupling of 6-pseudocuminol and preparing.Catalyst system is normally used for this linked reaction, and they comprise at least a heavy metal compound usually, as the compound of copper, manganese or cobalt, combines with other material usually.Non-functionalized poly arylene ether also can prepare by ready-formed poly (arylene ether) and bis-phenol reaction, randomly in the presence of the catalyzer (for example superoxide) that produces free radical, perhaps the reaction by high molecular poly (arylene ether) and quinhydrones or superoxide forms the lower molecular weight poly (arylene ether).
For the useful especially non-functionalized poly arylene ether of many purposes is that those comprise having the molecule that at least one contains the aminoalkyl group end group.Aminoalkyl group is usually located at the ortho position of hydroxyl.Can be by obtain to contain the product of this end group as a kind of component of oxidative coupling reaction mixture in conjunction with suitable uncle or secondary monoamine (for example two-n-Butyl Amine 99 or dimethylamine).4-Hydroxybiphenyl end group also often occurs, and obtains from reaction mixture usually, exists the by product biphenol to close quinone (diphenoquinone) in this reaction mixture, particularly in copper-halogenide-second month in a season or tertiary amine system.The cardinal principle ratio of polymer molecule usually by forming up to the polymkeric substance of about 90 weight %, can contain at least a in described end group that contains aminoalkyl group and the 4-Hydroxybiphenyl end group.The method of synthetic non-functionalized poly arylene ether homopolymer and multipolymer for example is described in people's such as the United States Patent (USP) 3,306,874 and 3,306,875 of Hay and Yonemitsu 4,011,200 and 4,038,343.
Poly (arylene ether) can be the functionalized poly arylene ether.Functionalized poly arylene ether resin comprises, for example, and end-blocking polyarylene ether resin and ring-functionalized poly arylene ether resin.
The end-blocking poly (arylene ether) can be represented by following structure,
Q(J-K)
y
Wherein Q is the residue of mono-hydroxy phenol, dihydric phenol or polyhydroxy phenol, and y is 1 to about 100; J comprises the repeated structural unit of following formula:
R wherein
1And R
3Be hydrogen, halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like; R
2And R
4Be halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like; M is 1 to about 200, is preferably 1 to about 100, more preferably 1 to 49; With K be capping group, be selected from
-Y-R
5，
R wherein
5Be C
1-C
12Alkyl; R
6-R
8Be hydrogen, C independently of one another
1-C
18Alkyl, C
2-C
18-oxyl carbonyl, nitrile, formyl radical, carboxylicesters, imidate, carbothioic acid ester or the like; R
9-R
13Be hydrogen, halogen, C independently of one another
1-C
12Alkyl, hydroxyl, amino, or the like; Wherein Y is selected from following divalent group:
R wherein
14And R
15Be hydrogen, C independently of one another
1-C
12Alkyl or the like.The term of Shi Yonging " alkyl " refers to only contain the residue of carbon and hydrogen herein.This residue can be aliphatic series or aromatics, straight chain, ring-type, branching, saturated or undersaturated.Yet when so defining hydrocarbyl residue, it can contain at carbon that replaces residue and the heteroatoms outside the hydrogen.Therefore, when particularly pointing out when containing this heteroatoms, hydrocarbyl residue also can contain carbonyl, amino, hydroxyl or the like, and perhaps it can contain the heteroatoms in the hydrocarbyl residue skeleton.Term herein " haloalkyl " comprises the alkyl that is replaced by one or more halogen atoms, comprises part and whole halogenated alkyl.
In one embodiment, Q is the phenol residue that comprises multifunctional phenol, and comprises the residue of following structure:
R wherein
1And R
3Be hydrogen, halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like; R
2And R
4Be halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like; X can be hydrogen, C
1-C
18Alkyl or contain the C of at least one substituting group (for example carboxylic acid, aldehyde, hydroxyl, amino)
1-C
18Alkyl, or the like; X also can be the bridged group of sulphur, sulfuryl, sulphonyl, oxygen or other divalent or higher valence state, two to obtain-or higher polyphenol; Y and n are 1 to about 100 independently of one another, are preferably 1 to 3, and more preferably about 1 to 2; In a preferred embodiment, y=n.Q also can be the residue of bis-phenol, for example 2,2 ', 6,6 '-tetramethyl--4,4 '-bis-phenol.
In one embodiment, the end-blocking poly (arylene ether) is for by with the ether capped product that obtains of polyarylene, and this poly (arylene ether) is made up of at least a polymerisate with mono-hydroxy phenol of following structure basically:
Wherein, R
1And R
3Be hydrogen, halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like; R
2And R
4Be halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl, wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl, or the like.Suitable mono-hydroxy phenol comprises those in the United States Patent (USP) 3,306,875 that is described in Hay, and highly preferred mono-hydroxy phenol comprises 2,6-xylenol and 2,3,6-pseudocuminol.Poly (arylene ether) can be at least two kinds of mono-hydroxy phenol, for example 2, and 6-xylenol and 2,3, the multipolymer of 6-pseudocuminol.
In one embodiment, the end-blocking poly (arylene ether) comprises that at least one has the capping group of following structure:
R wherein
6-R
8Be hydrogen, C independently of one another
1-C
18Alkyl, C
2-C
12-oxyl carbonyl, nitrile, formyl radical, carboxylicesters, imidate, carbothioic acid ester or the like.Highly preferred capping group comprises acrylate (R
6=R
7=R
8=hydrogen) and methacrylic ester (R
6=methyl, R
7=R
8=hydrogen).
In another embodiment, the end-blocking poly (arylene ether) comprises the capping group of structure below at least one:
R wherein
5Be C
1-C
12Alkyl is preferably C
1-C
6Alkyl, more preferably methyl, ethyl or propyl group.Even do not have polymerizable functionalities, for example during carbon-to-carbon double bond, also can obtain the advantageous property of composition at the end-blocking poly (arylene ether).
In another embodiment, the end-blocking poly (arylene ether) comprises that at least one has the capping group of following structure:
R wherein
9-R
13Be hydrogen, halogen, C independently of one another
1-C
12Alkyl, hydroxyl, amino, or the like.The preferred capping group of the type comprises salicylate (R
9=hydroxyl, R
10-R
13=hydrogen).
In another embodiment, the end-blocking poly (arylene ether) comprises the capping group of structure below at least one:
Wherein A is saturated or unsaturated C
2-C
12Bivalent hydrocarbon radical, for example ethylidene, propylene, 1,3-propylidene, 2-methyl isophthalic acid, 3-propylidene, 2,2-dimethyl-1,3-propylidene, 1,2-butylidene, 1,3-butylidene, 1,4-butylidene, 2-methyl isophthalic acid, 4-butylidene, 2,2-dimethyl-1,4-butylidene, 2,3-dimethyl-tetramethylene, vinylene (CH=CH-), 1,2-phenylene or the like.These end-blocking polyarylene ether resins usually can be by for example, the reaction of not end capped poly (arylene ether) and cyclic anhydride end-capping reagent and preparing.This cyclic anhydride end-capping reagent for example comprises, maleic anhydride, succinyl oxide, Pyroglutaric acid, adipic anhydride, phthalate anhydride or the like.
Be not particularly limited for the method for preparing the end-blocking poly (arylene ether).Can be by the prepared in reaction end-blocking poly (arylene ether) of not end capped poly (arylene ether) and end-capping reagent.End-capping reagent comprises the document compound known with the reaction of phenolic group group.These compounds comprise monomer and polymkeric substance, and described polymkeric substance for example contains, acid anhydride, acyl chlorides, epoxy, carbonic ether, ester, isocyanic ester, cyanate or alkyl halide residue.End-capping reagent is not limited to organic compound, also comprises for example Phosphorus and sulphur class end-capping reagent.The example of end-capping reagent comprises; diacetyl oxide for example; succinyl oxide; maleic anhydride; the bigcatkin willow acid anhydrides; comprise the unitary polyester of salicylate; salicylic equal polyester; acrylic anhydride; methacrylic anhydride; glycidyl acrylate; glycidyl methacrylate; Acetyl Chloride 98Min.; Benzoyl chloride; diphenyl carbonate (for example carbonic acid two (4-nitrophenyl) ester); the acryloyl ester; the methacryloyl ester; the ethanoyl ester; the phenyl cyanide acid esters; 3-pseudoallyl-α; the alpha-alpha-dimethyl phenyl isocyanate; cyanato-benzene; 2; two (the 4-cyanato-phenyl) propane of 2-); 3-(α-chloromethyl) vinylbenzene; 4-(α-chloromethyl) vinylbenzene; bromination allyl group or the like, carbonic ether and substitutive derivative thereof; and their mixture.These and other method that forms the end-blocking poly (arylene ether) for example is described in people's such as Holoch United States Patent (USP) 3,375,228; 4,148,843 of Goossens; People's such as Percec 4,562,243,4,663,402,4,665,137,4,701,514,4,871,876 and 5,091,480; People's such as Nelissen 5,071,922,5,079,268,5,304,600 and 5,310,820; People's such as Vianello 5,338,796; People's such as Yeager 6,352,782; People such as Braat 6,384,17 in; People's such as people's such as Yeager U.S. Patent application 2001/0053820 and Peters European patent 261,574B1.
In a preferred embodiment, the end-blocking poly (arylene ether) can react in the alkenyl aromatic monomer solvent by not end capped poly (arylene ether) and acid anhydride and make.The advantage of this method is can be immediately to obtain the end-blocking poly (arylene ether) with the form of other composition blend, to form curable compositions.Use this method, do not need to separate the end-blocking poly (arylene ether) or remove unwanted solvent or reagent.
In the reaction of not end-blocking poly (arylene ether) and acid anhydride, can use the end-blocking catalyzer.This examples for compounds comprise known in the art can the catalysis of phenol class and those of above-mentioned end-capping reagent condensation.The available material is a basic cpd, for example comprises basic cpd hydroxide salt, for example sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxide or the like; Alkyl amine, for example tributylamine, triethylamine, dimethyl benzyl amine, dimethylbutyl amine or the like; Mix tertiary alkyl-arylamines (tertiary mixedalkyl-arylamines) and substitutive derivative thereof, N for example, accelerine; Heterocyclic amine, for example imidazoles, pyridine, and substitutive derivative, for example glyoxal ethyline, 2-vinyl imidazole, 4-(dimethylamino) pyridine, 4-(1-pyrrole Lip river quinoline base) pyridine, 4-(1-piperidino-(1-position only)) pyridine, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine or the like.Also available is an organic metal salt, and for example, known catalysis is the pink salt and the zinc salt of isocyanic ester or cyanate and phenols condensation for example.In this respect, useful organic metal salt is known in the various publications known of those of ordinary skills and the patent.
The functionalized poly arylene ether can be a ring-functionalized poly arylene ether.In one embodiment, ring-functionalized poly arylene ether is the poly (arylene ether) that comprises the following formula repeated structural unit:
Each L wherein
1-L
4Be hydrogen, C independently
1-C
12Alkyl, C
2-C
12Alkenyl or C
2-C
12Alkynyl; Wherein alkenyl is expressed from the next:
L wherein
5-L
7Be that hydrogen or methyl and a are 0 to 4 integer (that is, 0,1,2,3 or 4) independently; Wherein alkynyl is expressed from the next:
L wherein
8For hydrogen, methyl or ethyl and b are 0 to 4 integer (promptly 0,1,2,3 or 4); Whole L in the ring-functionalized poly arylene ether wherein
1-L
4Substituent about 0.02 mole of % extremely about 25 moles of % is alkenyl and/or alkynyl.In this scope, preferably have at least about 0.1 mole of %, more preferably at least about alkenyl and/or the alkynyl of 0.5 mole of %.In this scope, can preferably have equally, more preferably up to alkenyl and/or the alkynyl of about 10 moles of % up to about 15 moles of %.
In another embodiment, the functionalized poly arylene ether is poly (arylene ether) and α, and the fusant reaction product of beta-unsaturated carbonyl compound or beta-hydroxy carbonyl compound is with preparation acid or anhydride-functionalized poly arylene ether.In some embodiments, can exist acid and the anhydride functional group the two.α, the example of beta-unsaturated carbonyl compound comprise for example various derivatives and similar compound of fumaric acid, toxilic acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride and aforesaid compound.The example of beta-hydroxy carbonyl compound comprises for example citric acid, oxysuccinic acid or the like.Usually to about 290 ℃ temperature, implement this functionalization about 190 by melt-mixing poly (arylene ether) and required carbonyl compound.
Composition can comprise the blend of at least two kinds of functionalized poly arylene ethers.Can prepare this blend by independent preparation and isolating functionalized poly arylene ether.Perhaps, this blend can be by reacting single poly (arylene ether) and at least two kinds of functionalized reagents make.For example, poly (arylene ether) can react with two kinds of end-capping reagents; Perhaps poly (arylene ether) can metallize and with two kinds of unsaturated alkyl reagent reacts.In another kind was selected, at least two kinds of mixtures with polyarylene ether resin of different monomers composition and/or molecular weight can react with single functionalized reagent, to obtain the blend of at least two kinds of functionalized poly arylene ethers.
The functionalized poly arylene ether also comprises following poly (arylene ether), it contains the part for preparing by grafting vinyl monomers or polymkeric substance (for example polystyrene), and comprise the link coupled poly (arylene ether), wherein coupling agent for example low-molecular polycarbonate, quinhydrones, heterocycle and methylal in a known way with the hydroxyl reaction of two poly (arylene ether) chains, obtain high-molecular weight polymer.
Molecular weight or limiting viscosity for poly (arylene ether) are not particularly limited.The number-average molecular weight of poly (arylene ether) (Mn) can be for about 1,000 to about 100,000 awus (AMU).In one embodiment, can to comprise data molecular weight (Mn) be about 10, the 000 non-functionalized poly arylene ethers to about 50,000 awus (AMU) to composition.In this scope, the Mn value of non-functionalized poly arylene ether can be preferably at least about 15,000.Equally in this scope, the Mn value of non-functionalized poly arylene ether can be preferably up to about 30,000AMU, more preferably up to about 25,000AMU.In another embodiment, can to comprise number-average molecular weight be about 8, the 000 functionalized poly arylene ethers to about 25,000 awus (AMU) to composition.In this scope, it is about 10 preferably to use number-average molecular weight to be at least, 000AMU, and more preferably at least about 15, the functionalized poly arylene ether of 000AMU.
When measuring, the limiting viscosity of poly (arylene ether) can be preferably about 0.05 to about 0.6dL/g for about 0.02 to about 1.5 deciliter/gram (dL/g) in 25 ℃ of chloroforms.In one embodiment, can to contain limiting viscosity be about 0.1 to about 1.0dL/g non-functionalized poly arylene ether to composition.In this scope, functionalized poly arylene ether limiting viscosity can be preferably at least about 0.2dL/g, more preferably 0.3dL/g at least.In this scope, the limiting viscosity of functionalized poly arylene ether can be preferably up to about 0.6dL/g, more preferably up to about 0.5dL/g equally.When in another embodiment, composition can comprise limiting viscosity and measures in 25 ℃ of chloroforms is the about 0.1 functionalized poly arylene ether to about 0.6 deciliter/gram (dL/g).In this scope, the limiting viscosity of functionalized poly arylene ether can be preferably at least about 0.2dL/g, more preferably 0.25dL/g at least.In this scope, the limiting viscosity of functionalized poly arylene ether can be preferably up to about 0.5dL/g, more more preferably up to about 0.4dL/g equally.Usually, the limiting viscosity of functionalized poly arylene ether will can the noticeable change with the limiting viscosity of corresponding non-functionalized poly arylene ether.Particularly, the limiting viscosity of functionalized poly arylene ether usually non-functionalized poly arylene ether limiting viscosity 10% in.At least two kinds of blends with functionalized poly arylene ether of different molecular weight and limiting viscosity are used in special expection.
Poly (arylene ether) comprises the arbitrary combination of above-mentioned non-functionalized and functionalized poly arylene ether resin.
Composition can comprise about 5 poly (arylene ether)s to about 95 weight parts, based on 100 weight part functionalized poly arylene ethers and the total amount that condenses alicyclic (methyl) acrylate monomer.In this scope, the consumption of preferred poly (arylene ether) is at least about 10 weight parts, more preferably at least about 20 weight parts, more preferably at least about 30 weight parts, more preferably at least about 35 weight parts.In this scope, the consumption of preferred poly (arylene ether) is up to about 90 weight parts, more preferably up to about 80 weight parts, more preferably up to about 70 weight parts equally.
Curable compositions comprises and condenses alicyclic (methyl) acrylate monomer.In one embodiment, this condenses alicyclic (methyl) acrylate monomer and has following formula:
Each R wherein
18Be C independently
1-C
12Alkylidene group, C
1-C
12The alkylidene group that hydroxyl replaces, or the like; Each R
19Be divalent group, for example C independently
1-C
18Alkylene, oxygen (O-), sulphur (S-), carbonyl (C (=O)-), thiocarbonyl (C (=S)-), sulfoxide group (S (=O)-), alkylsulfonyl (S (=O) 2-) and amine (N (R
22)-, be R wherein
22Be hydrogen or C
1-C
18Alkyl), or the like; Each r is 0 to about 12 independently; Each R
20And R
21Be hydrogen, C independently
1-C
12Alkyl or the like; With each s be 0 or 1 or 2 independently, condition is that the s that at least once occurs is at least 1.Be appreciated that R
18The alkylidene group that alkylidene group or hydroxyl replace can be straight chain, side chain or cyclic.In a preferred embodiment, R
1Be C
1-C
4Alkylidene group.Should be appreciated that, when r greater than 1 the time, R
19Can be identical or different when repeatedly occurring.For example, if s is 2, R
19Can be carbonyl when once occurring, and another time R when occurring
19Can be amine, thus for two contiguous R that occur
19Formed amido linkage.Therefore, R
19Repeatedly appearance can be used to form acid amides, ester, carbothioic acid ester, carbonic ether, sulphonamide, urea and sulphonyl ammonia bonding or the like.In one embodiment, each R
20Be hydrogen or methyl, each R
21Be hydrogen.In another embodiment, each r is 0.
Suitable condensing alicyclic (methyl) acrylate monomer for example comprises, 3 α-(methyl) acryloxy perhydro-indenes, 3 α-(methyl) acryloxy-7 Alpha-hydroxy perhydro-indenes, 3 α, 7 α-two [(methyl) acryloxy] perhydro-indenes, 4 α-(methyl) acryloxy naphthane, 4 α, 8 α-two [(methyl) acryloxy] naphthane, 4 α-(methyl) acryloxy perhydro-fluorenes, 4 α-(methyl) acryloxy-9 Alpha-hydroxy perhydro-fluorenes, 4 α, 9 α-two [(methyl) acryloxy] perhydro-fluorenes, 4 α-(methyl) acryloxy perhydroanthracene, 4 α-(methyl) acryloxy-9 Alpha-hydroxy perhydroanthracene, 4 α, 9 α-two [(methyl) acryloxy] perhydroanthracene, 10 α-(methyl) acryloxy perhydrophenanthrene, 10 α-(methyl) acryloxy-4 Alpha-hydroxy perhydrophenanthrene, 4 α, 10 α-two [(methyl) acryloxy] perhydrophenanthrene, 2-(methyl) acryloxy three ring [5.2.1.0
2,6] decane, 2-(methyl) acryloxy-6-hydroxyl three ring [5.2.1.0
2,6] decane, 2,6-two [(methyl) acryloxy] three ring [5.2.1.0
2,6] decane, 2,5-two [(methyl) acryloxy] three ring [5.2.1.0
2,6] decane, 2 α-(methyl) acryloxy perhydro acenaphthene, 2 α-(methyl) acryloxy-8 Alpha-hydroxy perhydro acenaphthene, 2 α, 8 α-two [(methyl) acryloxy] perhydro acenaphthene, 3 α-(methyl) acryloxy] the perhydro acenaphthene, 3 α-(methyl) acryloxy-9 Alpha-hydroxy perhydro acenaphthene, 3 α, 9 α-two [(methyl) acryloxy] perhydro acenaphthene or the like, and the aforementioned combination that condenses alicyclic (methyl) acrylate monomer.
In one embodiment, condense alicyclic (methyl) acrylate monomer and have following formula:
Each R wherein
23Be hydrogen or methyl independently.In preferred embodiment, R
23Be methyl.
Composition comprises about 5 to condensing of about 95 weight parts alicyclic (methyl) acrylate monomer, based on 100 weight part poly (arylene ether)s and the total amount that condenses alicyclic (methyl) acrylate monomer.In this scope, the amount that condenses alicyclic (methyl) acrylate monomer can be preferably at least about 10 weight parts, more preferably at least about 20 weight parts, more preferably at least about 30 weight parts.In this scope, the amount that condenses alicyclic (methyl) acrylate monomer can be preferably up to about 70 weight parts, more preferably up to about 65 weight parts equally.
Curable compositions can randomly further comprise alkenyl aromatic monomer.Alkenyl aromatic monomer can have following structure:
Each R wherein
16Be hydrogen or C independently
1-C
18Alkyl; Each R
17Be halogen, C independently
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
6-C
18Aryl, or the like; P is 1 to 4; With q be 0 to 5.The position that does not limit on the aromatic ring is replaced by hydrogen atom.Suitable alkenyl aromatic monomer comprises, for example, vinylbenzene, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-butyl styrene, 1,3-Vinylstyrene, 1,4-Vinylstyrene, 1,3-di isopropenylbenzene, 1, have on 4-di isopropenylbenzene, the aromatic ring 1 to 5 halogenic substituent vinylbenzene, or the like, and the combination.Preferred alkenyl aromatic monomer is a vinylbenzene.When existing, the consumption of alkenyl aromatic monomer can be for about 10 to about 1000 weight parts, based on 100 weight part poly (arylene ether)s with condense the total amount of alicyclic (methyl) acrylate monomer.In this scope, the alkenyl aromatic monomer amount can be preferably at least about 20 weight parts, more preferably at least about 40 weight parts.In this scope, the alkenyl aromatic monomer amount can be preferably up to about 500 weight parts, more preferably up to about 200 weight parts equally.
Curable compositions can randomly further comprise curing catalysts, to improve the solidification rate of unsaturated component.Curing catalysts is also referred to as initiator, is well known in the art, is used for initiated polymerization, solidifies or crosslinked a large amount of thermoplasticity and thermosetting material, comprises unsaturated polyester, vinyl ester and allylic thermosetting material.The non-limiting example of curing catalysts is to be described in following those: " PlasticAdditives Handbook, 4
Th.Edition " R.Gachter and H.Muller (eds.), P.P.Klemchuck (assoc.ed.) Hansen Publishers, New York 1993, and people such as people's such as Smith United States Patent (USP) 5,407,972 and Katayose 5,218,030.The curing catalysts that is used for the unsaturated part of thermosetting material can comprise any compound that can at high temperature produce free radical.These curing catalysts can comprise peroxide and non-peroxide radical initiator.The example of useful peroxy initiator for example comprises; benzoyl peroxide; dicumyl peroxide; methyl-ethyl-ketone peroxide; lauryl peroxide; cyclohexanone peroxide; tert-butyl hydroperoxide; the tert.-butylbenzene hydroperoxide; the sad fat of t-butyl peroxy; 2; 5-dimethylhexane-2; the 5-dihydro-peroxidase; 2; 5-dimethyl-2; 5-two (t-butyl peroxy)-oneself-3-alkynes; two-tert-butyl peroxide; tertiary butyl cumyl peroxide; α; α '-two (t-butyl peroxy--sec.-propyl) benzene; 2; 5-dimethyl-2; 5-two (t-butyl peroxy) hexane; dicumyl peroxide; the di-tert-butyl peroxide isophthalic acid ester; tert butyl peroxy benzoate; 2; two (t-butyl peroxy) butane of 2-; 2; two (t-butyl peroxy) octanes of 2-; 2; 5-dimethyl-2; 5-two (benzoyl peroxide) hexane; two (trimethyl silyl) superoxide; trimethyl silyl phenyl triphenyl silyl superoxide or the like, and the mixture that comprises at least a aforementioned curing catalysts.Typical non-peroxy initiator for example comprises, 2, and 3-dimethyl-2,3-diphenyl butane, 2,3-trimethyl silyl oxygen base-2,3-diphenyl butane or the like, and the mixture that comprises at least a aforementioned curing catalysts.The curing catalysts that is used for the unsaturated part of thermosetting material may further include any compound that can cause unsaturated component anionoid polymerization.These anionic polymerization catalysts for example comprise, basic metal metal amide, for example sodium amide (NaNH
2) and diethylamino lithium (LiN (C
2H
5)
2); C
1-C
10An alkali metal salt of alkoxide and ammonium salt; Alkali metal hydroxide and ammonium hydroxide; Alkali metal cyanide; Organometallic compound, for example alkyl lithium compounds n-Butyl Lithium and Grignard reagent phenyl-magnesium-bromide or the like, and the combination that comprises at least a aforementioned anionic polymerization catalyst.
In a preferred embodiment, curing catalysts can comprise tert butyl peroxy benzoate or methyl-ethyl-ketone peroxide.Curing catalysts can promote to solidify down at about 0 ℃ to about 200 ℃.
When existing, the consumption of curing catalysts can be for about 0.1 to about 10 weight parts, based on 100 parts of whole poly (arylene ether)s with condense alicyclic (methyl) acrylate monomer.In this scope, the curing catalysts amount that can preferably use is at least about 0.5 weight part, more preferably at least about 1 weight part.In this scope, the amount that can preferably use curing catalysts is up to about 5 weight parts, more preferably up to about 3 weight parts equally.
Curable compositions can comprise further randomly that curing catalyst is to reduce gel time.Suitable curing catalyst comprises transition metal salt and complex compound, for example naphthalene diacid cobalt; And organic bases, N for example, accelerine (DMA) and N, N-Diethyl Aniline (DEA).Preferably combination is used naphthalene diacid cobalt and DMA.When existing, the consumption of curing catalyst can be about 0.05 to about 3 parts, based on 100 parts of whole poly (arylene ether)s with condense alicyclic (methyl) acrylate monomer.
Composition may further include one or more fillers, comprises particulate filler and fibrous packing.The example of these fillers known in the art comprises and is described in " Plastic Additives Handbook, 4
ThEdition " R.Gachter and H.Muller (eds.), P.P.Klemchuck (assoc.ed.) HansenPublishers, those fillers among the New York 1993.Particulate filler is defined as average aspect ratio less than about 5: 1 filler herein.The non-limiting example of filler comprises silica powder, for example fused silica and crystalline silica; Boron nitride powder and borosilicate powder are used to obtain to have the cured product of low-k and low-dielectric loss angle tangent; Above-mentioned powder and aluminum oxide and magnesium oxide (or magnesia) are used for high temperature conductivity; And filler, for example wollastonite comprises the surface-treated wollastonite; Calcium sulfate (its anhydride, dihydrate or trihydrate); Lime carbonate comprises chalk, Wingdale, marble and synthetic, precipitated chalk, with the form of abrasive grains, generally comprises 98+%CaCO usually
3, surplus is other inorganics, for example magnesiumcarbonate, ferric oxide and pure aluminium silicate; Surface-treated lime carbonate; Talcum comprises fibrous, block, needle-like and stratiform talcum; Glass sphere, hollow or solid and surface-treated glass sphere has coupling agent (for example silane coupling agent) usually and/or contains conductive coating; And kaolin, comprise hard, soft kaolin and comprise the kaolin of various coatings known in the art, to promote dispersion in thermosetting resin or compatible with thermosetting resin; Mica, comprise the metallization mica and with the surface-treated mica of aminosilane or acryl silane coating to give composite blend good rerum natura; Feldspar and nephelinite syenite; The silicate ball; Cigarette ash; Hollow particle; The inert silicate microballoon; Pure aluminium silicate (armospheres) comprises silanization and metallized pure aluminium silicate; Natural silica Sand; Quartzy; Quartzite; The natural pearls rock; Tripoli (Tripoli); Diatomite; Synthetic silica comprises the synthetic silica with various silane coatings, or the like.
Preferred particulate filler comprises that mean particle size about 1 is to about 10 microns lime carbonate.In this scope, mean particle size can be at least about 2 microns, or at least about 3 microns.Equally in this scope, mean particle size can be up to about 8 microns, or up to about 7 microns.
Fibrous packing comprises inorganic staple fibre, comprises the mineral fibre of processing, for example derives from those that comprise blend at least a in pure aluminium silicate, aluminum oxide, magnesium oxide and the calcium sulfate hemihydrate.The fibrous packing that also comprises is that single crystal fibre or " whisker " comprise silicon carbide, aluminum oxide, norbide, carbon, iron, nickel, copper.The fibrous packing that also comprises is a glass fibre, comprises glasscloth, for example E, A, C, ECR, R, S, D and NE glass and quartz.Preferred fibrous packing comprise diameter be about 5 to about 25 microns and compound before length be about 0.5 to about 4 centimetres glass fibre.Many other appropriate filler are described among people's such as Yeager the U.S. Patent application 2001/0053820A1.
Prescription can also contain adhesion promotor, to improve the binding property of thermosetting resin and filler or exterior coating or substrate.Can also handle aforementioned mineral filler with adhesion promotor, so that binding property to be provided.Adhesion promotor comprises chromium complex, silane, titanate, zirconium aluminate, propylene maleic anhydride copolymers, the plain ester of reactive fibre or the like.Chromium complex comprises that DuPont is with trade mark VOLANT
Those that sell.Silane comprises that formula is (RO)
(4-n)SiY
nMolecule, n=1-3 wherein, R is an alkyl or aryl, Y is a reactive functional groups, this functional group can form key with polymer molecule.Useful especially coupling agent example is for having (RO)
3Those of SiY structure.Representative instance comprises vinyl-triethoxyl silane, vinyl three (2-methoxyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrimewasxysilane and γ-Qiu Jibingjisanjiayangjiguiwan.Titanate comprises people such as S.J.Monte in Ann.Chem.Tech Conf.SPI (1980), Ann.Tech Conf.Reinforced Plastics and Composite Inst.SPI 1979, Section 16E, those that develop among the NewOrleans; And S.J.Monte, Mod.Plastics Int., volume 14, those that develop among the number6 pg.2 (1984).
Zirconium aluminate comprises L.B.Cohen at Plastics Engineering, and volume 39, and number 11, those that describe among the page 29 (1983).Adhesion promotor can be included in the thermosetting resin itself, perhaps is coated on aforementioned any filler to improve the binding property between filler and the thermosetting resin.For example, can use this adhesion promotor silicon-coating silicate fiber or filler to improve the binding property of resin matrix.
In a preferred embodiment, filler comprises lime carbonate.In another preferred embodiment, filler comprises glass fibre.In highly preferred embodiment, filler comprise lime carbonate and glass fibre the two.
When existing, the usage quantity of particulate filler can be for about 5 to about 80 weight %, based on the gross weight of composition.In this scope, the usage quantity of preferred particulate filler is at least about 1 weight %, more preferably at least about 20 weight %, and also more preferably at least about 30 weight %, even more preferably at least about 40 weight %.In this scope, the usage quantity of preferred particulate filler is up to about 70 weight %, more preferably up to about 60 weight % equally.Perhaps, the amount of particulate filler can be expressed as about 5 to about 1000 weight parts, based on 100 weight part poly (arylene ether)s and the total amount that condenses alicyclic (methyl) acrylate monomer.
When existing, the consumption of fibrous packing can be for about 2 to about 80 weight %, based on the gross weight of composition.In this scope, the consumption of optimum fiber filler is at least about 5 weight %, more preferably at least about 10 weight %, and also more preferably at least about 15 weight %, even more preferably at least about 20 weight %.In this scope, the consumption of optimum fiber filler is up to about 60 weight %, more preferably up to about 40 weight %, also more preferably up to about 30 weight % equally.Perhaps, the fibrous packing amount can be expressed as about 5 to about 1000 weight parts, based on 100 weight part poly (arylene ether)s and the total amount that condenses alicyclic (methyl) acrylate monomer.
Aforementioned filler can be added thermosetting resin and do not carry out any processing, or add in surface treatment (handling with adhesion promotor usually) back.
Curable compositions can randomly further comprise one or more additives known in the art, for example dyestuff, pigment, tinting material, oxidation inhibitor, thermo-stabilizer, photostabilizer, softening agent, lubricant, flow ability modifying agent, fire retardant, anti-drops, anti-hard caking agent, static inhibitor, flow improver additive, processing aid or the like, with and combination.Those skilled in the art can select suitable additive and determine suitable consumption.
A kind of embodiment is a curable compositions, comprising: the end capped poly (arylene ether) of methacrylic ester and have condensing of following formula alicyclic (methyl) acrylate monomer:
Each R wherein
23Be hydrogen or methyl independently.
Another embodiment is a curable compositions, comprising: about 5 to the end capped poly (arylene ether) of about 95 parts by weight of methacrylate; About 5 have condensing of following formula alicyclic (methyl) acrylate monomer to about 95 weight parts:
Each R wherein
23Be hydrogen or methyl independently; About 50 lime carbonate to about 600 weight parts; With about 50 glass fibre to about 600 weight parts.
Be not particularly limited for the preparation method for compositions.Can comprise that poly (arylene ether) and the even blend that condenses alicyclic (methyl) acrylate monomer prepare composition by formation.When composition comprises that alkenyl aromatic monomer and poly (arylene ether) are the end-blocking poly (arylene ether), can directly obtain composition in the following manner: not end capped poly (arylene ether) is dissolved in the part alkenyl aromatic monomer from non-functionalized poly arylene ether, in the presence of alkenyl aromatic monomer, add end-capping reagent and form the end-blocking poly (arylene ether), condense alicyclic (methyl) acrylate monomer and any other component with adding, form thermoset composition.
Method for curing composition is not particularly limited.Can or use radiotechnology by for example thermofixation, for example comprise that uv-radiation and electron beam shine and curing composition.When using thermofixation, selected temperature can be about 80 ° to about 300 ℃.In this scope, can be preferably at least about 120 ℃ temperature.Equally in this scope, can be preferably up to about 240 ℃ temperature.Can be about 30 seconds to about 24 hours heat-up time.In this scope, be at least about 1 minute preferred heat-up time of using, more preferably at least about 2 minutes.Equally in this scope, preferred heat-up time of using is up to about 10 hours, and more preferably about 5 hours, also more preferably up to about 3 hours.Can carry out this curing by stages, to prepare partly solidified and often inadherent resin, then with this resin by longer time of heating or be heated to temperature in the above-mentioned scope and completely solidified.
A kind of embodiment is to obtain cured compositions by solidifying any foregoing curable composition.Because the component of curable compositions may be reacted each other in the solidification process, cured compositions can be described as comprising the reaction product that obtains by the cure curable compositions component.Therefore, a kind of embodiment is a cured compositions, comprises by curing comprising the reaction product that poly (arylene ether) and the composition that condenses alicyclic (methyl) acrylate obtain." curing " and " solidified " comprises partly solidified for example to form so-called B-rank composition to should be appreciated that term.Another embodiment is a cured compositions, comprises the reaction product of following material: the end capped poly (arylene ether) of methacrylic ester; And have condensing of following formula alicyclic (methyl) acrylate monomer:
Each R wherein
23Be hydrogen or methyl independently.Another embodiment is a cured compositions, comprises solidifying the reaction product that following material obtains: about 5 to the end capped poly (arylene ether) of about 95 parts by weight of methacrylate; About 5 have condensing of following formula alicyclic (methyl) acrylate monomer to about 95 weight parts
Each R wherein
23Be hydrogen or methyl independently; About 50 lime carbonate to about 600 weight parts; With about 50 glass fibre to about 600 weight parts.
Another embodiment comprises the goods of any cured compositions.Curable compositions can be used for making a large amount of goods.Can comprise from the goods of composition manufacturing, for example, acid bath container, neutralizing well, the electrorefining groove, the water-softening agent groove, fuel tank, winding filament groove (filament-wound tanks), the winding filament tank lining, electrolyzer, the exhaust bucket, washer, automobile exterior panel, chassis, automobile rear floor (automotivefloor pans), automotive air induction duct (air scoops), the truck bed lining, transmission shaft, the transmission shaft coupling device, the tractor parts, transverse sheet spring (transverse leaf spings), crankcase heater, heat shield, road tank car, the trolley cover, hull, the diving hull, the boat deck, sea-freight is the anti-side of a ship (marine terminalfenders) in station eventually, aircraft component, propeller blade, the guided missile assembly, the rocket engine shell, wing section (wingsection), pump rod, the fuselage cross section, aircraft wing panel (wing skins), wing nose cone (wing flairings), nacelle (engine narcelles), hatch door, aircraft stretching slide block (aircraft stretch block) and pneumatic hammer constitute (hammer forms), bridge, bridge floor, railing, rail, the walkway, pipeline, pipeline, fan guard, ceramic tile, building wall board (building panels), washing tower, the floor, the expansion of bridge connects, be used for repairing and repairing the fissured plaster that injects of structural concrete, ceramic tile is expected with grouting, the machinery handrail, metallic pin, bolt, post (post), the electronic seal agent, switchboard, printed circuit board, electric component, wrapping wire (wire windings), the sealing of electrochemical appliance, battery container, resistance, insurance, thermal cut-out device (thermal cut-off devices), the coating that is used for printed circuit board, electric capacity, transformer, the conductive component that is used for antistatic application, tennis racket, golf club, fishing rod, sled, ski pole, bicycle assembly parts, swimming pool, the swimming pool slide plate, heat channel, Saunas, mixing tank, the vending machine shell, dish, dishwasher components, the refrigerator parts, furniture, garage door, fence, protector (protective body gear), luggage, optical waveguide (optical waveguides), nose cone (radomes), satellite antenna, annunciator, solar panels, the telephony switching gear cover, transformer casing, the insulation of rotary machine, rectifier, core insulation (core insulation), the dry toner resin, bonding fixture, check fixture (inspectionfixture), the Industrial Metal forming mould, vacuum moulding mould or the like.The matrix material that composition is specially adapted to make printed circuit board, encapsulation compositions, potting compound and is used for electrical isolation.
Composition exhibiting goes out the height favorable properties.For example composition can demonstrate second-order transition temperature at least about 110 ℃ behind molding.As another example, composition can demonstrate thermal expansivity up to about 75ppm (parts per million) after being lower than the second-order transition temperature molding, measures according to ASTM D6341.Cured compositions can also demonstrate dissipation factor (according to ASTM D150, under 25 ℃ and 1 kilohertz or 10 kilohertzs or 100 kilohertzs or 1 megahertz, measure) be less than or equal to 0.02, be preferably and be less than or equal to 0.01, more preferably be less than or equal to 0.005.In one embodiment,, be less than or equal to 0.005 at 25 ℃, the dissipation factor of the cured compositions under 1 kilohertz and 10 kilohertzs and 100 kilohertzs and 1 megahertz, measured respectively according to ASTMD150.
Further explain the present invention by following indefiniteness embodiment.
Preparation embodiment 1
The step that the embodiment 1 of people's such as use Yeager U.S. Patent application 2001/0053820A1 describes prepares methacrylic ester end capped poly-(2,6-dimethyl-1, the 4-phenylene ether), its limiting viscosity in 25 ℃ of chloroforms is that 0.25dL/g and residual hydroxyl content are that 136.22 micromoles-OH/ restrains poly (arylene ether).Simply,, use the methanol extraction product, filter also drying and prepare this compound by reaction non-functionalized poly (2,6-dimethyl-1,4-phenylene ether) and methacrylic anhydride and dimethyl aminopyridine in toluene solvant.Methacrylic ester end capped poly-(2,6-dimethyl-1,4-phenylene ether) is dissolved in the vinylbenzene, forms 35 weight % solution.
Embodiment 1-4
Will be from the methacrylic ester of preparation embodiment 1 end capped poly-(2,6-dimethyl-1,4-phenylene ether) and three ring [5.2.1.0
2,6] the decane dimethanol is with the blend of ratio shown in the table 1.The tert butyl peroxy benzoate that in every kind of solution, adds 2 weight parts.120 ℃ of compression moulding said compositions 8 minutes and 5,000 pounds of/square inch compression moulding 8 minutes, obtain disk samples.On compression moulded samples, measure various character.Determine second-order transition temperature (Tg) and thermal expansivity (CTE) according to ASTM D6341.Measure the CTE value being lower than and being higher than under the second-order transition temperature.Measure kick off temperature and remaining percentage ratio by thermogravimetric analysis (TGA).Composition (represent with weight part, pbw) is summarized in the table 1 with character by content.Data show that the composition exhibiting that comprises poly (arylene ether) and condense aliphatic series (methyl) acrylic compound goes out high glass transition temperature and low thermal coefficient of expansion.
Table 1
| Ex.1 | Ex.2 | Ex.3 | Ex.4 | |
| Composition | ||||
| End capped PPE solution, 35% in vinylbenzene (pbw) | 80 | 75 | 70 | 65 |
| Three ring [5.2.1.0 2.6] decane dimethanol diacrylate (pbw) | 20 | 25 | 30 | 35 |
| Tert butyl peroxy benzoate (pbw) | 2 | 2 | 2 | 2 |
| Character | ||||
| Tg(℃) | 115 | 113 | 118 | 122 |
| CTE＜T g(ppm) | 72 | 74 | 74 | 74 |
| CTE＜T g(ppm) | 207 | 211 | 218 | 223 |
| TGA decomposition beginning (℃) | 408 | 404 | 413 | 407 |
| TGA remnants (wt%) | 4.5 | 4.2 | 4.7 | 3.6 |
Embodiment 5, Comparative Examples 1
The styrene solution of 35% methacrylic ester end capped poly-(2,6-dimethyl-1,4-phenylene ether) is heated to about 70-80 ℃ and also stirs until becoming fluid.With three ring [5.2.1.0
2,6] decane dimethanol diacrylate adds with the amount shown in the table 2, and solution is cooled to 50 ℃.Add tert butyl peroxy benzoate and violent stirring solution.Gained resin cool to room temperature also solidifies at 150 ℃ and 5000psi plus-pressure.Use Viscoat 295 to replace three ring [5.2.1.0
2,6] decane dimethanol diacrylate prepares reference examples.According to ASTM D150, under 1,10 and 100 kilohertzs and 1 megahertz, measure dissipation factor.Composition and character are shown in table 2.Result's demonstration is compared with the composition of the Comparative Examples 1 with Viscoat 295, and the composition exhibiting with embodiment 5 of alicyclic acrylate goes out consistently and obvious lower dissipation factor.
Table 2
| Embodiment 5 | Comparative Examples 1 | |
| Composition | ||
| End-blocking PPE solution, 35% in vinylbenzene (pbw) | 80 | 80 |
| Three ring [5.2.1.0 2，6] decane dimethanol diacrylate (pbw) | 20 | 0 |
| Viscoat 295 (pbw) | 0 | 20 |
| Tert butyl peroxy benzoate (pbw) | 2 | 2 |
| Character | ||
| Dissipation factor under 1 kilo hertz | 0.0013 | 0.120 |
| Dissipation factor under 10 kilo hertzs | 0.0019 | 0.0182 |
| Dissipation factor under 100 kilo hertzs | 0.0020 | 0.0042 |
| Dissipation factor under 1 megahertz | 0.0034 | 0.0046 |
Though described the present invention, it should be understood by one skilled in the art that to change or its key element is carried out equivalence to replace, and do not depart from the scope of the present invention with reference to preferred implementation.In addition, can carry out multiple improvement so that instruction of the present invention adapts to specific occasion or material, and not break away from essential scope of the present invention.Therefore, the present invention is not intended to limit the specific implementations that provides in as carrying out optimal desired mode of the present invention, but the present invention will comprise all embodiments that claim contains.
Be incorporated herein by reference in full at this patent, patent application and other reference all references.
Claims (9)
1. curable compositions comprises:
Poly (arylene ether); With
Condense alicyclic (methyl) acrylate monomer,
Wherein said poly (arylene ether) is to prepare by the method that comprises at least a monohydroxy aromatics of oxidative coupling, wherein poly (arylene ether) is the functionalized poly arylene ether, and wherein the functionalized poly arylene ether is the end-blocking poly-(arylene ether) with following structure
Q(J-K)
y
Wherein Q is the residue of mono-hydroxy phenol, dihydric phenol or polyhydroxy phenol, and y is 1 to 100;
J comprises the repeated structural unit of following formula:
R wherein
1And R
3Be hydrogen, halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl or wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl; R
2And R
4Be halogen, uncle or secondary C independently of one another
1-C
12Alkyl, C
2-C
12Alkenyl, C
2-C
12Alkynyl, C
1-C
12Aminoalkyl group, C
1-C
12Hydroxyalkyl, phenyl, C
1-C
12Haloalkyl, C
1-C
12-oxyl or wherein at least two carbon atoms separate the C of halogen atom and Sauerstoffatom
2-C
12The halo-oxyl; M is 1 to 200; With
K is a capping group, is selected from
R wherein
5Be C
1-C
12Alkyl; R
6-R
8Be hydrogen, C independently of one another
1-C
18Alkyl, C
2-C
18-oxyl carbonyl, nitrile, formyl radical, carboxylicesters, imido-ester or carbothioic acid ester; R
9-R
13Be hydrogen, halogen, C independently of one another
1-C
12Alkyl, hydroxyl or amino; Wherein Y is selected from following divalent group:
R wherein
14And R
15Be hydrogen or C independently of one another
1-C
12Alkyl.
2. the curable compositions of claim 1, wherein the functionalized poly arylene ether is the end-blocking poly-(arylene ether) with following structure,
Q(J-K)
y
Wherein Q is the residue of mono-hydroxy phenol or dihydric phenol, and y is 1 or 2;
J comprises the repeated structural unit of following formula:
R wherein
1And R
3Be hydrogen, uncle C independently of one another
1-C
12Alkyl; M is 1 to 200; R
2And R
4Be uncle C independently of one another
1-C
12Alkyl; With
K is a structure
Capping group
R wherein
6-R
8Be hydrogen or C independently of one another
1-C
18Alkyl.
3. the curable compositions of claim 1 is 0.05 to 0.6 deciliter/gram when wherein the limiting viscosity of poly (arylene ether) is measured in 25 ℃ of chloroforms.
4. the curable compositions of claim 1 comprises the poly (arylene ether) of 5 to 95 weight parts, based on 100 weight part poly (arylene ether)s with condense the total amount of alicyclic (methyl) acrylate monomer.
5. the curable compositions of claim 1 wherein condenses alicyclic (methyl) acrylate monomer and has following formula:
Wherein, each R
18Be C independently
1-C
12Alkylidene group or C
1-C
12The alkylidene group that hydroxyl replaces; Each R
19Be divalent group independently, be selected from C
1-C
18Alkylene, oxygen (O-), sulphur (S-), carbonyl (C (=O)-), thiocarbonyl (C (=S)-), sulfoxide group (S (=O)-), alkylsulfonyl (S (=O)
2-) and general formula be-N (R
22)-amine, R wherein
22Be hydrogen or C
1-C
18Alkyl; Each r is 0 to 12 independently; Each R
20And R
21Be hydrogen or C independently
1-C
12Alkyl; With each s be 0 or 1 or 2 independently, condition is that the s that at least once occurs is at least 1.
6. the curable compositions of claim 1 wherein condenses alicyclic (methyl) acrylate monomer and has following formula:
Each R
23Be hydrogen or methyl independently.
7. the curable compositions of claim 1 comprises condensing of 5 to 95 weight parts alicyclic (methyl) acrylate monomer, based on 100 weight part poly (arylene ether)s and the total amount that condenses alicyclic (methyl) acrylate monomer.
8. the curable compositions of claim 1 further comprises alkenyl aromatic monomer.
9. the curable compositions of claim 1, wherein composition exhibiting goes out at least 110 ℃ second-order transition temperature behind molding.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/637,943 US7226980B2 (en) | 2003-08-07 | 2003-08-07 | Thermoset composition, method for the preparation thereof, and articles prepared therefrom |
| US10/637,943 | 2003-08-07 |
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| US (2) | US7226980B2 (en) |
| EP (1) | EP1654323A1 (en) |
| JP (1) | JP2007501876A (en) |
| KR (1) | KR20060040607A (en) |
| CN (1) | CN100396729C (en) |
| WO (1) | WO2005017036A1 (en) |
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| US7211639B2 (en) * | 2003-10-03 | 2007-05-01 | General Electric Company | Composition comprising functionalized poly(arylene ether) and ethylene-alkyl (meth)acrylate copolymer, method for the preparation thereof, and articles prepared therefrom |
| US7329708B2 (en) * | 2004-08-18 | 2008-02-12 | General Electric Company | Functionalized poly(arylene ether) composition and method |
| US7700670B2 (en) | 2005-05-13 | 2010-04-20 | Beach Brian A | Low-density molding compound |
| US20070066710A1 (en) * | 2005-09-21 | 2007-03-22 | Peters Edward N | Method for electrical insulation and insulated electrical conductor |
| US20070107632A1 (en) * | 2005-10-28 | 2007-05-17 | Ball Richard L | Pigmented wall and ceiling spackle |
| US20070208159A1 (en) * | 2006-03-02 | 2007-09-06 | General Electric Company | Poly(arylene ether) block copolymer compositions, methods, and articles |
| US20080097069A1 (en) * | 2006-10-20 | 2008-04-24 | Hua Guo | Poly(arylene ether) method and composition |
| US7723420B2 (en) * | 2008-07-25 | 2010-05-25 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis and polymerization of oligomeric divinyl-terminated aromatic ether-containing resins |
| CN107418173A (en) | 2014-06-27 | 2017-12-01 | 赛史品威奥（唐山）结构复合材料有限公司 | The low-density moulded material for the microsphere being modified including surface |
| US9508549B2 (en) | 2014-12-26 | 2016-11-29 | Dow Global Technologies Llc | Methods of forming electronic devices including filling porous features with a polymer |
| CN109482724A (en) * | 2018-11-02 | 2019-03-19 | 福建南平南孚电池有限公司 | Steel shell of alkaline cell forming production line and its remodeling method |
| JPWO2022080403A1 (en) * | 2020-10-16 | 2022-04-21 |
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-
2003
- 2003-08-07 US US10/637,943 patent/US7226980B2/en not_active Expired - Fee Related
-
2004
- 2004-06-29 CN CNB2004800175532A patent/CN100396729C/en not_active Expired - Fee Related
- 2004-06-29 KR KR1020057025154A patent/KR20060040607A/en not_active Application Discontinuation
- 2004-06-29 EP EP04756339A patent/EP1654323A1/en not_active Withdrawn
- 2004-06-29 WO PCT/US2004/020868 patent/WO2005017036A1/en active Application Filing
- 2004-06-29 JP JP2006522559A patent/JP2007501876A/en not_active Ceased
-
2005
- 2005-01-05 US US11/029,819 patent/US7199213B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5965663A (en) * | 1995-06-06 | 1999-10-12 | Kabushiki Kaisha Toshiba | Resin composition and resin-molded type semiconductor device |
| US6306963B1 (en) * | 2000-05-08 | 2001-10-23 | General Electric Co. | Thermosetting resins and laminates |
| US20020177027A1 (en) * | 2001-01-18 | 2002-11-28 | Yeager Gary William | Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| US7199213B2 (en) | 2007-04-03 |
| US20050032979A1 (en) | 2005-02-10 |
| CN1809614A (en) | 2006-07-26 |
| KR20060040607A (en) | 2006-05-10 |
| EP1654323A1 (en) | 2006-05-10 |
| US20050137307A1 (en) | 2005-06-23 |
| US7226980B2 (en) | 2007-06-05 |
| JP2007501876A (en) | 2007-02-01 |
| WO2005017036A1 (en) | 2005-02-24 |
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